Opening the black box of mixed-metal TMP metallating reagents : direct cadmation or lithium-cadmium transmetallation?
Armstrong, David R. and Kennedy, Alan and Mulvey, Robert E. and Parkinson, John A. and Robertson, Stuart D. (2012) Opening the black box of mixed-metal TMP metallating reagents : direct cadmation or lithium-cadmium transmetallation? Chemical Science, 3 (9). pp. 2700-2707. ISSN 2041-6539 (https://doi.org/10.1039/c2sc20392h)
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Abstract
Designed to remove some of the mystery surrounding mixed-metal TMP (2,2,6,6-tetramethylpiperidide) metallating reagents, this study examines in detail "LiCd(TMP)(3)'' in its own right. Previously established as an excellent "cadmating'' (Cd-H exchange) reagent towards a wide variety of aromatic substrates, "LiCd(TMP)(3)'' has been investigated by H-1, C-13 and Cd-113 NMR studies as well as by DOSY NMR spectroscopy. This evidence puts a question mark against its ate formulation implying it exists in THF solution as two independent homometallic amides. Exploring the reactivity of "LiCd(TMP)(3)'' with anisole as a test substrate, both experimentally by NMR studies and theoretically by DFT studies suggests a two-step lithiation/transmetallation process in which the initially formed ortho-lithiated species undergoes a reaction with Cd(TMP)(2) to form new Cd-C and Li-N bonds. For completeness, the homometallic cadmium component Cd(TMP)(2) has been comprehensively characterised for the first time including a crystal structure determination revealing a near-linear N-Cd-N arrangement.
ORCID iDs
Armstrong, David R., Kennedy, Alan ORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, Robert E. ORCID: https://orcid.org/0000-0002-1015-2564, Parkinson, John A. ORCID: https://orcid.org/0000-0003-4270-6135 and Robertson, Stuart D. ORCID: https://orcid.org/0000-0002-9330-8770;-
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Item type: Article ID code: 41338 Dates: DateEvent2012Published5 July 2012Published OnlineSubjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 03 Oct 2012 13:26 Last modified: 04 Sep 2024 00:47 URI: https://strathprints.strath.ac.uk/id/eprint/41338